TiO2负载硅胶催化剂的制备和光催化活性

用溶胶-凝胶法制备Fe3+、Gd3+共掺杂的纳米TiO2,并以硅胶(SiO2)为载体制备出负载型催化剂(Fe3+/Gd3+/TiO2-SiO2)。用X射线衍射仪(XRD)、扫描电镜(SEM)和紫外漫反射(DRS)等手段对其进行了表征。研究了溶胶煅烧温度、煅烧时间以及陈化时间对硅胶负载效果及对亚硝酸盐的光催化活性的影响,并测定了催化剂的用量及其循环使用对亚硝酸盐的光催化活性的影响。结果表明,与Fe3+/Gd3+/TiO2相比,负载型催化剂可显著提高催化剂的光催化活性;在500℃煅烧2 h、陈化时间1 h、催化剂投入量为1.0 g/L时亚硝酸盐降解效果最佳,降解率约为90.46%。     

Fe~(3+)/Al~(3+)-TiO_2复合光催化剂的制备及其光催化性能研究

以钛酸四正丁酯为先驱物,采用溶胶-凝胶法制备铁铝共掺杂的TiO2(Fe3+/Al3+-TiO2)复合光催化剂,并用XRD、UV-Vis等进行表征,系统研究煅烧温度、光催化体系中的盐对Fe3+/Al3+-TiO2复合光催化剂在自然光条件下光催化降解甲基橙性能的影响。结果表明,Fe3+/Al3+-TiO2光催化降解甲基橙的性能随着煅烧温度的升高而增强,催化体系中的HCO3-和NO2-使Fe3+/Al3+-TiO2复合光催化剂的催化活性有所降低。     

负载型纳米TiO_2的制备及其对亚硝酸盐的光催化活性的研究

采用溶胶-凝胶法制备了Fe3+、Gd3+共掺杂纳米TiO2,并以空心玻璃微珠(HGM)为载体制备了负载型催化剂(Fe3+/Gd3+/TiO2-HGM)。用X射线衍射仪(XRD)、扫描电镜(SEM)和紫外漫反射(DRS)对其进行了表征。考察了溶胶煅烧温度、煅烧时间对空心微珠负载效果的影响,并对负载次数、催化剂用量对亚硝酸盐的光催化活性的影响进行了测定。结果表明,与自制Fe3+/Gd3+/TiO2相比,负载型催化剂可显著提高催化剂的光催化活性;当以500℃下煅烧2h,负载两次,催化剂投入量为2.0g/L时,亚硝酸盐可得到最大降解,其降解率约为93.81%。     

磁性La3+掺杂TiO2的制备及性能

利用溶胶-凝胶法,在室温条件下,以钛酸四丁酯、硝酸镧为主要原料,无水乙醇为溶剂,冰醋酸为抑制剂,浓硝酸为催化剂制得稳定的掺La3+TiO2溶胶,陈化后的凝胶经不同温度煅烧3h后制得不同掺La3+量的TiO2。通过XRD对不同煅烧温度及不同掺La3+量的TiO2进行了表征;以紫外光为光源,研究了掺La3+-TiO2对甲基橙溶液的光降解效果。用化学共沉淀法制备了具有强磁性的Fe3O4水基磁流体,再与La3+掺杂TiO2进行复合,制备了Fe3O4负载量不同的磁性La3+掺杂TiO2,研究了Fe3O4负载量不同的La3+掺杂TiO2对甲基橙的光催化降解效果、磁分离回收率的影响。结果表明,掺La3+量及煅烧温度对TiO2的晶型、各晶型TiO2的相对含量及对甲基橙的光降解效果均有影响。La3+掺杂TiO2比纯TiO2显示出更强的光催化性能,掺La3+量2%,热处理温度450℃的La3+掺杂TiO2光催化活性最高。Fe3O4负载量为10%的Fe3O4/La3+-TiO2对甲基橙的降解率8h时为99.4%;磁分离回收率达97.39%。     

双微乳液法制备掺杂Fe~(3+)的纳米TiO_2及其光催化性能

为了研究双微乳液法在制备纳米级光催化剂的应用,以TiCl4和NH3.H2O为原料,采用十六烷基三甲基溴化铵-正丁醇-环己烷-水微乳体系制备Fe3+掺杂纳米TiO2,对粉末的晶体结构进行X射线衍射表征,并以其对p-甲酚的降解考察其光催化活性。结果表明,在较小的掺杂量时,Fe3+掺杂量的提高可以提高TiO2的光催化活性,进一步提高掺杂量将引起光催化活性的降低;掺杂Fe3+可导致纳米TiO2的粒径减小;Fe3+的半径较小以及Fe2O3的熔点较低均有利于TiO2从锐钛矿向金红石的相变;当Fe3+掺杂摩尔分数为0.06%,煅烧温度为550℃时,纳米TiO2的光催化活性最高,此时形成TiO2的锐钛矿和金红石相的混晶;乳液中含水量也会影响晶相的组成和粒径大小,随着含水量增加产物中出现了一定比例的金红石相。     

静电纺丝法制备Fe3+/TiO2纳米纤维及表征

以聚乙烯吡咯烷酮(PVP)为纤维模板,钛酸四丁酯(Ti[O(CH2)3CH3]4)和Fe3+为前驱体,乙醇为溶剂,醋酸为催化剂,采用静电纺丝法制备不同含铁量的复合纳米纤维Fe3+/TiO2,经500℃煅烧得到以锐钛矿为主的Fe3+/TiO2纳米纤维。采用扫描电子显微镜(SEM)和X射线衍射仪(XRD)分别表征了Fe3+/TiO2纳米纤维的形貌与晶态,计算了样品的晶粒尺寸和锐钛矿所占的比例,并比较了5%Fe3+/TiO2纳米纤维、5%Fe3+/TiO2粉体以及纯TiO2纳米纤维三者光催化降解亚甲基蓝(MB)的效果。研究表明:由静电纺丝法制备的5%Fe3+/TiO2纳米纤维的光催化降解效果比相同含铁量的粉体的降解效果好,TiO2纳米纤维比5%Fe3+/TiO2纳米纤维的光催化活性高。     

Ag~+/TiO_2-ZnO纳米复合薄膜的制备及双亲性能

采用溶胶-凝胶法制备了TiO2薄膜、TiO2-ZnO纳米薄膜和Ag+/TiO2-ZnO纳米薄膜。通过X射线衍射和原子力显微镜表征了样品的晶相、晶粒尺寸和形貌。以水(H2O)作为极性溶液参照物、苯(C6H6)作为非极性溶液参照物,研究了掺杂量、煅烧温度、表面处理对薄膜光致双亲性的影响。结果表明:在ZnO/TiO2复合薄膜中,适量掺杂Ag+会提高其双亲性,摩尔比为1%时最佳。煅烧温度的不同能够导致薄膜的晶粒粒径、晶型及薄膜表面的粗糙度发生变化,从而影响薄膜的双亲性能。煅烧温度为550℃、经酸溶液或热处理后Ag+/TiO2-ZnO纳米薄膜的双亲性最佳,其晶粒粒径约为21.1nm。此时,亲水角和亲油角分别为2°和0.5°。Ag+/TiO2-ZnO纳米薄膜的双亲性明显高于纯TiO2和TiO2-ZnO纳米薄膜。     

Fe_3O_4/Ce~(3+)-TiO_2复合光催化材料的制备及其光催化性能研究

采用溶胶-凝胶法,以钛酸四丁酯、硝酸铈为主要原料,无水乙醇为溶剂,冰醋酸为抑制剂,浓硝酸为催化剂制得稳定的Ce3+掺杂TiO2溶胶,其凝胶经不同温度煅烧3 h后制得Ce3+掺杂量不同的TiO2粉体。用XRD对TiO2进行了测试对比分析,以紫外光为光源,亚甲基蓝溶液为模拟有机染料废水,研究了TiO2的光催化性能。用化学共沉淀法制备了具有强磁性的纳米Fe3O4水基磁流体,再与Ce3+掺杂TiO2进行复合,制备了Fe3O4负载量不同的磁性Ce3+掺杂TiO2,研究了其对亚甲基蓝的光催化降解效果、磁分离回收率的影响。结果表明,TiO2凝胶热处理温度、Ce3+掺量、TiO2晶型及Fe3O4负载量对亚甲基蓝的光催化活性均有影响。掺Ce3+量为1%,热处理温度650℃的Ce3+掺杂TiO2粉体光催化活性最高。Fe3O4负载量为10%的Fe3O4/Ce3+-TiO2对亚甲基蓝的降解率8 h时达到90.3%,磁分离回收率达96.8%。     

Eu3+和Sm3+共掺杂TiO2光催化剂的协同效应

采用溶胶-凝胶法制备了纯TiO2和Eu3+/Sm3+共掺杂TiO2复合粉体,采用XRD,DRS和SEM等技术进行表征,以亚甲基蓝(methylene blue,MB)的光催化降解为目标反应,评价了其光催化活性,探讨了Eu3+/Sm3+共掺杂对TiO2粉体光催化的影响机制.结果表明,Eu3+/Sm3+共掺杂可以显著提高TiO2粉体光催化活性,Eu3+/Sm3+共掺杂在TiO2粉体中产生协同作用,可以抑制TiO2由锐钛矿相向金红石相转变,使TiO2的粒径减小.Eu3+/Sm3+共掺杂增大了TiO2粉体的晶格畸变,使TiO2粉体吸收带边蓝移.当Eu3+/Sm3+的掺杂量分别为0.05%和0.1%,TiO2光催化活性最高,光催化降解率达到84.8%.     

Ni2+掺杂TiO2光催化剂的制备及性能研究

选取Ni 2+掺杂量、冰醋酸、浓硝酸、煅烧温度设计正交实验,采用溶胶-凝胶法制备Ni 2+掺杂TiO2光催化剂,利用Raman、XRD、TEM等检测技术对其进行表征。通过与溶胶-凝胶法制备的纯TiO2纳米光催化剂进行对比,结果表明:Ni 2+掺杂TiO2光催化剂的TEM图像显示为球形粒子集合体,XRD图谱峰值降低,晶粒细化,拉曼光谱谱峰宽化、蓝移。以甲基橙模拟染料废水的降解率考察Ni 2+掺杂TiO2光催化活性,最佳条件下,Ni 2+掺杂TiO2对甲基橙的降解率为87.21%。     

微乳液法制备掺杂铁的纳米二氧化钛及其表征

为了研究掺杂铁的纳米二氧化钛的性质,以TiCl4为原料,在CTAB/正丁醇/环己烷/水组成的微乳液体系中制备了掺杂铁的TiO2纳米粉末。采用热分析仪(TG-DTA)、X射线衍射分析(XRD)、透射电子显微镜(TEM)和比表面分析仪(BET)等对粉体的结构、粒径大小、物相、形貌和比表面积等进行了表征。经600℃焙烧2h后,0.04%Fe3+-TiO2粉末为单一的锐钛型结构,其平均晶粒度约为16nm,比表面积达120.4m2.g-1,D101为16.1nm。由于在XRD图谱上未发现有新相的生成,因此,Fe3+经过焙烧渗入到了二氧化钛的晶格中,掺杂所引起的变化主要是由于Fe3+渗入TiO2晶格所引起的。     

热处理工艺对多孔TiO2薄膜光催化性能的影响

以十八胺为模板剂,采用溶胶-凝胶法在玻璃基体上制备了多孔TiO2薄膜,研究了热处理工艺对薄膜理化性质及光催化性能的影响。随煅烧温度和煅烧时间的增加,TiO2薄膜表面逐渐形成清晰的孔结构,晶粒尺寸增大。薄膜由锐钛矿型TiO2组成,Ti以Ti 4+的形式存在。制备的TiO2薄膜厚度在200nm左右,薄膜的UV-Vis透射率随煅烧温度的升高呈下降趋势,随煅烧时间的延长先下降而后又上升。多孔TiO2薄膜光催化降解甲基橙结果表明,随煅烧温度升高薄膜的光催化活性增加,在500℃煅烧2h制备的薄膜具有最佳的光催化活性。     

掺铁二氧化钛纳米线的合成及其光催化性能

首次以钛酸丁酯、异丙醇等有机物为原料,在10M NaOH溶液中水解后,于180℃水热24h,一步法合成二氧化钛纳米线(TNWs),并用扫描电子显微镜(SEM)和X射线衍射(XRD)等手段表征其形貌和结构。结果表明,所得TNWs焙烧到950℃时,仍为锐钛矿相,表明本制备方法迟滞了二氧化钛由锐钛矿相到金红石相的转变。此外,以甲基橙为目标降解物,在300 W汞灯照射下,研究了不同水热温度、保温时间及掺杂量对掺铁二氧化钛纳米线(Fe-TNWs)光催化性能的影响。结果表明,于750℃焙烧4h制备的掺铁摩尔百分数为0.5%的TNWs,具有最强的光催化降解性能,其降解速率和效率较未掺杂的样品都有了大幅度的提高。     

Preparation of Fe3+-doped TiO2 catalysts by controlled hydrolysis of titanium alkoxide and study on their photocatalytic activity for methyl orange degradation

Fe3+-doped TiO2 (Fe-TiO2) porous microspheres were prepared by controlled hydrolysis of Ti(OC4H9)4 with water generated "in situ" via an esterification reaction between acetic acid and ethanol, followed by hydrothermal treatment. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic absorption flame emission spectroscopy (AAS), electron paramagnetic resonance (EPR) spectrum, X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), and nitrogen adsorption-desorption methods. All of the undoped TiO2 and Fe-TiO2 samples exclusively consist of primary anatase crystallites, which further form porous microspheres with diameters ranging from 150 to 500 nm. The photocatalytic activity of Fe-TiO2 catalysts was evaluated from the photodegradation of methyl orange (MO) aqueous solution both under UV and visible light irradiation. Fe3+ doping effectively improves the photocatalytic activity under both UV light irradiation and visible light irradiation with an optimal doping concentration of 0.1 and 0.2%, respectively. The photocatalytic mechanisms of Fe-TiO2 catalysts were tentatively discussed.     

Solvothermal synthesis of crystalline phase and shape controlled Sn(4+)-doped TiO2 nanocrystals: effects of reaction solvent

The Sn(4+)-doped TiO(2) nanocrystals with controlled crystalline phase and morphology had been successfully prepared through easily adjusting the solvent system from the peroxo-metal-complex precursor by solvothermal method. The Sn(4+)-doped TiO(2) nanocrystals were characterized by XRD, Raman, TEM, HRTEM, XPS, ICP-AES, BET, and UV-vis. The experimental results indicated that the Sn(4+)-doped TiO(2) nanocrystals prepared in the pure water or predominant water system trend to form rodlike rutile, whereas the cubic-shaped anatase Sn(4+)-doped TiO(2) nanocrystals can be obtained in the alcohol system. The growth mechanism and microstructure evolution of the Sn(4+)-doped TiO(2) nanocrystals prepared in the different solvent systems are discussed. The liquid-phase photocatalytic degradation of phenol was used as a model reaction to test the photocatalytic activity of the synthesized materials. It was found that sample Sn(4+)-doped TiO(2) prepared in 1-butanol showed the maximum photoactivity, which attributed to higher band gap, optimal crystalline phase and surface state modifications.     

SnP2+-TiO2的可见光催化活性及其在介孔蒙脱石上的负载

分别以氯化锡和氯化亚锡为Sn源,使用溶胶-凝胶法制备出不同掺杂量的Sn-TiO2,比较了Sn2+与Sn4+对掺杂后TiO2可见光催化活性的影响.实验结果显示,Sn2+与Sn4+均能显著抑制TiO2晶粒生长,并促进其晶型转变.但Sn2+-TiO2的可见光催化活性却明显优于Sn4+-TiO2,这主要是Sn2+外层半充满的电子轨道结构引起的.将可见光催化活性很高的Sn2+-TiO2负载于大比表面积、高稳定性的介孔蒙脱石上,由于载体与Sn-TiO2之间发生了相互作用,负载后样品的UV-Vis光谱吸收边相对于Sn-TiO2发生了显著红移,且可见光催化活性也有大幅提高.     

Photocatalytic oxidation of nitric oxide with immobilized titanium dioxide films synthesized by hydrothermal method

Gas-phase photocatalytic oxidation (PCO) of nitric oxide (NO) with immobilized TiO2 films was studied in this paper. The immobilized TiO2 films were synthesized by hydrothermal method. The characterization for the physicochemical properties of catalysts prepared under different hydrothermal conditions were carried out by X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), Brunauer-Emmett-Teller measurements (BET) and scanning electron micrograph (SEM). It was found that the PCO efficiency of the catalyst was mainly depended on the hydrothermal conditions. The optimal values of hydrothermal temperature and hydrothermal time were 200 degrees C and 24 h, respectively. Furthermore, it was also known that the photocatalytic efficiency would decrease remarkably when the calcination temperature was over than 450 degrees C. Under the optimal conditions (hydrothermal condition: 200 degrees C for 24 h; calcination temperature: 450 degrees C), the photocatalytic efficiency of catalyst could reach 60% higher than that of Degussa P25.     

Preparation and characterization of magnetically separable photocatalyst (TiO2/SiO2/Fe3O4): effect of carbon coating and calcination temperature

TiO2/SiO2/Fe3O4 composite was synthesized by sol-gel technique for silica and titania coatings on magnetite core to enable recovery after photocatalytic degradation. Carbon coating was also carried out by calcination of TiO2/SiO2/Fe3O4 under nitrogen atmosphere in presence of PVA as a source of carbon to enhance the adsorption of organic compounds on catalyst surface and to get better activity. All prepared samples were characterized using EDX, CN analyzer, XRD, BET and SEM. Degradation of methyl orange dye was used to assess the photocatalytic performance of the prepared samples. Calcination temperature was found to affect rate of reaction because of the formation of rutile phase at high calcination temperature. Carbon coated samples unexpectedly exhibited lower rate of reaction at almost all calcination temperatures.     

溶胶-凝胶法制备TiO2粉体及其光催化性能研究

以钛酸丁酯为前驱物,无水乙醇为溶剂,采用溶胶-凝胶法制备了TiO2粉体,并采用紫外分光光度计、XRD等表征手段对TiO2的粒度、晶型结构进行了表征,分析了煅烧温度、TiO2晶型比例、溶液初始pH值等因素对TiO2结构性能及光催化活性的影响.结果表明:TiO2的锐钛矿晶型与金红石晶型的转相温度为700 ℃左右;采用溶胶-凝胶法制备TiO2时,控制溶液的pH值为4,煅烧温度为600 ℃,所得产物晶型全部为锐钛矿;当无水乙醇与钛酸丁酯的体积比为10:1时,产物的粒径为617 nm;且当配制溶液pH值为4,煅烧温度为600℃条件下,煅烧时间为40~60 min时,所制备TiO2的光催化效果较好,降解率较高;当光催化体系的pH值为9、以质量浓度为10 mg/L的亚甲基兰溶液浸泡2 h,TiO2的用量为0.25 g/L时,产物的降解率高达95.3%.